DOI | Trouver le DOI : https://doi.org/10.1039/c2cp40819h |
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Auteur | Rechercher : Brogaard, Rasmus Y.; Rechercher : Schalk, Oliver1; Rechercher : Boguslavskiy, Andrey E.1; Rechercher : Enright, Gary D.2; Rechercher : Hopf, Henning; Rechercher : Raev, Vitaly; Rechercher : Tarcoveanu, Eliza; Rechercher : Sølling, Theis I.; Rechercher : Stolow, Albert1 |
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Affiliation | - Conseil national de recherches du Canada. Technologies de sécurité et de rupture
- Conseil national de recherches du Canada. Science des mesures et étalons
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Format | Texte, Article |
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Résumé | The Paternò–Büchi (PB) reaction between an excited carbonyl compound and an alkene has been widely studied, but so far little is known about the excited-state dynamics of the reaction. In this investigation, we used a compound in which a formyl and a vinyl group are attached to a [2.2]paracyclophane in order to obtain a model system in pre-reactive conformation for the PB reaction. We studied the excited-state dynamics of the isolated molecule in a molecular beam using femtosecond time-resolved photoelectron spectroscopy and ab initio calculations. The results show that inter-system crossing within two picoseconds competes efficiently with the reaction in the singlet manifold. Thus, the PB reaction in this model system takes place in the triplet state on a time scale of nanoseconds. This result stresses the importance of triplet states in the excited-state pathway of the PB reaction involving aromatic carbonyl compounds, even in situations in which the reacting moieties are in immediate vicinity. |
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Date de publication | 2012-05-02 |
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Dans | |
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Langue | anglais |
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Publications évaluées par des pairs | Oui |
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Numéro NPARC | 21268938 |
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Exporter la notice | Exporter en format RIS |
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Signaler une correction | Signaler une correction (s'ouvre dans un nouvel onglet) |
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Identificateur de l’enregistrement | 74ec4d5a-837d-4b6e-bece-1f8d54c1f049 |
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Enregistrement créé | 2013-11-27 |
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Enregistrement modifié | 2020-04-21 |
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